Mixed ester composition and process of making the same



Patented Aug. 1932 a UNITED STATES PATENT OFFICE HERBERT HONEL, OI VIENNA, AUSTRIA, ASSIGNOR TO BECK, ROLLER & COMPANY, INC

/ OF DETROIT, MICHIGAN. A CORPORATION OF DELAWARE MIXED E STER COMPOSITION AND PROCESS OF MAKING THE SAME No Drawing.

The invention relates to the production of .mixed ester "compositions and to the process of making the same.

This application is a continuation in part of my application Serial No. 454,186, filed May 20, 1930, which in turn is a continuation in part of my prior application Serial No. 362,460, filed May 11, 1929, now Patent No. 1,800,296, dated April 24, 193 1.

Itis known to combine natural resins with condensation products obtained from phenols with aldehydes'and the like, by employing elevated temperatures. Products of special technical and economic importance '5 are apparently created by reacting fresh acid rosins (of conifers) together with relatively small amounts of low molecular phenol alcohols. As known, the latter are condensation products obtained by means of alkali from ,phenols and formaldehyde and are rendered insoluble when heated alone. When proper proportions and conditions are employed the .resulting products are clear and soluble in common solvents without residue. Their hardness and melting point are much higher thanthat of the rosin itself, but their acid value is still of corresponding value v to that of the rosin itself, and it has been suggested to esterify them. with alcoholic bodies as has been practiced a long time previously with acid rosins themselves. Such esterfied products also possess improved properties as compared with the common rosin esters themselves, such as increased toughness, hardness and melting point.

But it is a disadvantage of these products 1 that they are not compatible'with nitrocellulose, even if very small amounts only'of phenol alcohols have been employed.

I have formed new and very useful products by esterifying said reaction products of the acid rosin and phenol alcohols and a relatively low molecular carboxylic acid with a polyhydric alcohol. Doubtless mixed esters of t e polyhydric alcohol result from Application filed June 6,

this procedure. The relative increase of the ester groups by introducing such relatively low molecular carboxylic acid groups in the molecule apparently causes the compatibility withnitrocellulose. The Employment of acids of the aromatic series has been found to be superior to the use of acids of the aliphatic series. Furthermore it is evident that polybasic acids which still further increase the relative amount of ester groups therefore may be used advantageously. Theresulting esterlike products are also particularly tough and hard. The quantity of such acids employed must be limited, as otherwise insoluble masses might result. 7

\ Furthermore, Ihave advantageously employed these new resins in combination with drying vegetable oils to make a varnish. The

stituted by their fatty acids and the corresponding amount of glycerine. Of course, theoretically the whole amount of the oil may be substituted by its fatty acids, but this.

would he uneconomical. The resinlike solid products obtained according to my process are soluble in the usual mixtures of solvents for cellulose esters and generally also in benzol hydrocarbons, while their solubility in pe-' troleum hydrocarbons is mostly unsatisfactory. Products combined with fatty oils are mostly soluble in the cheap petroleum hydrocarbons, or at least in mixtures of thes with benzol hydrocarbons. The solutions themselves can be employed in the same way as common oil varnishes with driers, but they and allows the formation of very Tao the above described solid resins themselves. A simultaneous addition of plasticizers is superfluous when such products combined with fatty oils are employed. For such urposes products are 'very advantageousw ich are combined with castor oil. Castor oil readily enters into the chemical composition pale prod ucts.

The vterm low molecular as used in the specification and claims as applied to acids employed is intended to distinguish such acids from the relatively high molecular natural resin acids. 7 v v 4 A few examples may explain my process:

Example 1.A liquid phenol alcohol is formed from 150 parts of a technical mixture of m-p-cresol and 180 parts of formaldehyde (40 volume by means of alkali and'then introduced into 1000 parts of melted French rosin WG. The temperature of the melt is raised to a maximum of 210 O. A clear resin is obtained which has a melting point of about 100 to 110 C. and an acid number of about 140. 300 parts of benzoicacid and 200'parts ofglycerine (95%); areadded and the temperature raised under continued stir ring until a uniform reacting mass isobtained. Finally the esterification' is carried out at 270 C. The resulting resin has a rather low melting point, but is very tough and has very good adhesion. It is soluble in benzol hydrocarbonsa d'the usual mixtures of solvents for nitroc'e lulose and produces a clear film in connection with nitrocellulose in all proportions, showing many desirable properties.

Example 25-100 parts of WW arereacted with a liquid phenol alcohol obtained "from 12 parts of USP cresol and 135 parts of formaldehyde (540 volume as described in Example 1. The reacting prod- I not is esterified simultaneously with 20 parts of phthalic anhydride and 20 parts of glycerine. The resulting product has a melting point of 108*120? (Land anacid number of about 20 and is very hard and tough. Its color is light reddish brown. The color can be considerably improved, when phthalic anhydride and glycerine '(or at least part of the latter) are first heated alone until a stickyreaction product is formed which is practically free from phthalic anhydride and thisreaction' product is then combined 'with that resulting from the rosin and the phenol alcohols. The reaction product or phthalic anhydride and glycerine may show an acid number of-- 16O to 230, and is to be considered .as a partial ester which still contains free carboxylic and'alcoholic groups. The other properties are equal to those obtained by the American rosin.

products resulting from the first method. They are very adaptable both for use in nitro lacquers and in oil varnishes. In the latter case, they must be heated with, the drying oil or a part of it to about 260-280 C. to get a clear solution.

It should be mentioned that an 'esterlike product which is obtained from 20 parts of phthalic anhydride and 20 parts of glycerine and 100 parts of American rosin itself, (i. e. the same proportions employed as in Example 2, but without employing the phenol alcohol) lacks by far that hardness and toughbutyric acids does not leave the reacting mass.

The very pale, hard and tough final product is highly adaptable for use in nitrocellulose lacquers.

prepared as follows: To 100 parts of technical meta cresol which usually contains about 60% meta cresol and 40% para cresol are introduced carefully and under cooling parts of sulphuryl chloride. Under splitting off of S0 and HCl merely them -cresol 'will be chlorinated in the p-position, while the pcresol will remain untouched. After Washing and neutralizing the reaction product a condensation product is formed with 140 parts of formaldehyde (40 volume by means of alkali. The condensation product, which is a reddish oily and crystalline mass, is caused to react with 600 partsof Spanish crystal rosin in a manner as disclosed in the above examples. Afterwards 406 parts of phthalic anhydride, 280 parts of glycerine fand 100 parts of linseed oil fatty acids are 'added and. heated under stirring to about;

' Example 4.A condensation product is 200 C. When the reacting mass has become clear and uniform, 300 parts of linseed oil and 150 parts of China wood oil areslowly added, Then the temperature is raised to 260270 C. and held until the acid number is sufiiciently low and the mass shows the de; sired consistency. It is a very satisfactory base for varnishes and can also be incorporated in nitrocellulose lacquers'in'every proportion. w .It has-been found that by the use of phenols which are substituted in the position,

final products are formed of satisfactory light proofness.

E wample 5.-In

Example 4 the fatty acids 7 and 13 parts of glycerine, the linseed oil and the China 011 are-substituted'by450 parts of castor oil. The glycerine and the hthalic anhydride are first heated alone as escribed in Example 2 until the mass has an acid number of about 220." For the rest the same conditions are employed. The resulting prodnet is very pale and tough and can be used as a base for quick-drying enamelswith or with- V out addition of nitrocellulose.

It will be understood that the above description and specific examples are given by a 'way of-illustration rather than by way of table oils are mentioned, as illustrative of limitation and known equivalents of the sub stances .set forth may be substituted for those 'ven by way of illustration. Thus, while W W m'the examples set forth above, only vegethe fatty oils, it is contemplated that other h oils. Likewise, other substitutes other original or starting substances may be fatty oils "may be used, as for example, filslh or t e em loyed.

y' relatively low molecular carboxyhc acids 1 have reference to carboxylic acids such as butyric, benzoic, succinic, maleic,

adipic, phthalic, eamphoric, and citric which are crystalline in character as distinguished from relatively high molecular monobasic and polybasic acids such as natural resinous acids or fatty acids of either unaltered or polymerized natural glycerides having more or less colloidal properties as distinguished from crystalline. a What I claim is:

1. 'A process which comprisesesterifying the acid product obtained by the reaction of a fresh natural resin and phenol-alcohols by 1 combining with such acid product a relativei ly low molecularcarbox'ylic acid and 'poly- V hydricalcohol.

2. As a new c m ition of matter, an esterlike rea'ctioltpr net of (1) apolyhydric 7 not of a fresh natural resin acid and (3) phealcohol combined with (2) the reaction prodnol. alcohols and a relatively carboxylic acid. v 3. A product accordin to claim 2 which is combined with a fatty o' e 4. A product according'to claim 2 which low molecular is combined with a fatty oil of the drying I 5. A mixed ester of a polyhydric alcohol,

which'ester containsasacid groups ('1) the consisting of relatively my signature. 5

int

x no

reaction product of a-naturalresin acid with a phenol alcohol and (2) a relatively low molecular carboxylic acid and (3) the.acids of a fatty oil.

the reaction of 6. A new com(pos1tion ofmatter formed by Q phenol alcohol, (3) at least one member of a group consisting of relatively low molecular polybasic carboxylicacids and anhydrides,

and (4) a polyhydric alcohol.

7. A process of producing artificial masses which comprises acid, (2) a phenol; mlco o amatural resin acid, (2) a l) anaturalresin,

(3)-atleast one 

